Catalytic composition of matter

ABSTRACT

A composition of matter having high catalytic activity, especially for cracking hydrocarbons, is prepared by intimately mixing from 15 to 80 percent by weight of synthetically produced interstratified montmorillonite-mica-like silicate mineral, exemplified by that obtainable in accordance with U.S. Pat. Nos. 3,252,757 and 3,252,889; from 1 to 40 percent of faujasite, natural or synthetic, having a silica-to-alumina ratio within the range of about 3 to about 6 1/2; and from 5 up to about 70 percent of a silicate material chosen from the class consisting of kaolinite, metakaolinite, halloysite, metahalloysite, and montmorillonite, and mixtures thereof, said mixing being carried out in an aqueous slurry with the base-exchangeable components in their ammonium form, followed by drying and calcining and grinding.

United States Patent [1 1 Granquist Apr. 8, 1975 CATALYTIC COMPOSITIONOF MATTER [75] Inventor: William T. Granquist, Houston,

Tex.

[73] Assignee: NL Industries, Inc., New York, NY.

[22] Filed: Mar. 16, 1972 [2l] Appl. No.: 235,417

Primary E.\'aminerC. Dees Attorney, Agent, or Firm-Delmar H. Larsen; RoyF. House; Robert L. Lehman [5 7 ABSTRACT A composition of matter havinghigh catalytic activity, especially for cracking hydrocarbons, isprepared by intimately mixing from 15 to 80 percent by weight ofsynthetically produced interstratified montmorillonitemica-like silicatemineral, exemplified by that obtainable in accordance with US. Pat. Nos.3,252,757 and 3,252,889; from 1 to 40 percent of faujasite, natural orsynthetic, having a silica-to-alumina ratio within the range of about 3to about 6 /2; and from 5 up to about 70 percent of a silicate materialchosen from the class consisting of kaolinite, metakaolinite,halloysite, metahalloysite, and montmorillonite, and mixtures thereof,said mixing being carried out in an aqueous slurry with thebase-exchangeable components in their ammonium form, followed by dryingand calcining and grinding.

7 Claims, N0 Drawings CATALYTIC COMPOSITION OF MATTER This inventionrelates to novel compositions of matter having enhanced catalyticactivity, particularly for the catalytic cracking of hydrocarbons.

Catalysts have been employed for many years in the transformation ofcrude petroleum and its various components and derivatives, intoproducts of greater economic value for specific purposes. One of themost widely employed catalytic transformations of this general type isthe conversion of petroleum hydrocarbons having molecular weigthsgreater than the hydrocarbons comprising gasoline into products of lowermolecular weight useful as motor fuels of the gasoline type. Crackingcatalysts useful for this transformation have comprised natural clays,more or less amorphous alumina-silica materials, zeolitic minerals, andothers. The overall procedure is well known and need not be detailedhere. Those unfamiliar with the art will find adequate descriptions insuch books as Catalysis, P. H. Emmett, editor, Vol. 6, Chapter 5 (NewYork l958) and V0]. 7, Chapter 1 (New York 1960) and, Advances inCatalysis, W. G. Frankenberg et al., editors, Vol. 3, pp. 179-247, (NewYork l95l) and Vol. 4, pp. 1-30 and 88-149, (New York 1952).

The most widely employed procedure at the present time utilizes thecracking catalyst in particles small enough to form a fluidized bed. Anadequate description of this and closely related procedures may be foundin Petroleum Processing, May 1957, pp. 98 107.

No known cracking catalyst is free from practical disadvantages in use.For example, an ideal catalyst for gasoline production would cause allof the feed stock to be transformed into 100 percent gasolinehydrocarbons, without attrition, loss, or change in catalyticeffectiveness even though used indefinitely. Needless to say. the knowncommercial catalysts fall considerably short of the ideal. Specificfigures will be given hereinbelow, but it may be stated that in thepresent state of the art a catalyst manufacturer considers himselffortunate if he can produce a catalyst which will transformsubstantially more than one-half of the feed stock into a highpercentage of usable gasoline hydrocarbons; and a similar statementholds for other desired products.

An object of the present invention is to provide a composition of matterwhich is particularly useful as a catalyst and especially so forhydrocarbon cracking, of a nature which gives excellent gasoline yields,and moreover which represents an enhanced effectiveness of any of thecomponents taken separately.

Other objects of the invention will appear as the description thereofproceeds.

A useful catalyst has been provided by the invention developmentdescribed in U.S. Pat. Nos. 3,252,757 and 3,252,889. These patents teachthe production, by hydrothermal synthesis. of a laminar claylike i.e.clay type mineral, as described more fully in the cited patents, andwhich represents a mixed layer structure having randomly alternatinglayers of montmorillonitelike and mica-like clay mineral. That inventionproduct has excellent utility as a hydrocarbon cracking catalyst, andquantitative test results will be found in the two patents cited.

The laminar clay-like mineral described in the aforesaid patents has asilica-to-alumina ratio within the range of 2.4 to 3.0. The mineralcompositions within this range represent a distinct species within agroup having at least two members. The other species of which l am awarehas a silica-to'alumina ration within the range of less than 2.4 butmore than 1.8. As will appear in greater detail hereinbelow, memberswithin each of the two species may be distinguished by their swellingbehavior with ethylene glycol.

Even the materials just described can however be improved as catalysts,and more particularly as cracking catalysts, in accordance with thepresent invention. Generally speaking, and in accordance withillustrative embodiments of the invention, I produce an intimate mixtureof from 1 to 40 percent (by weight) of faujasite, which may be naturalor synthetic, having a silicaalumina ratio within the range of about 3to about 6 /2 with from about 15 to about percent of either of thesynthetic clay-like minerals just described or mixtures of the two inany proportions, and from 5 up to about 70 percent of a silicatesubstance chosen from the class exemplified by kaolinite, metakaolin,halloysite, metahalloysite, and montmorillonite, and mixtures thereof,all as more fully described below.

Continuing with the general description of the inventive procedure, Iplace the selected synthetic clay mineral or mixture thereof and thefaujasite in their ammonium forms, if not already therein, together withthe selected silicate substance or mixture thereof, and slurry them inwater, and agitate the slurry so that a thoroughly homogeneous blend isproduced. The synthetic clay mineral and the faujasite are ofexceedingly fine particle size, predominantly finer than about threemicrons in size; and the additional silicate substance (or mixture ofseveral thereof) is likewise dispersed to the same order of magnitude.After a homogeneous slurry is produced by this mixing process, theslurry is dried to produce the inventive catalyst material. I have foundspray drying to be best, since this enables particles of roughlyspherical shape to be produced all within the optimum particle sizerange for fluid-bed catalytic cracking (FCC) which is approximately 20to microns. However, the slurry may be dried by other means, such as ona heated drum, and later ground by any of the usual methods to produce apowder of any desired fineness. Various additional additives or treatingagents, particularly in accordance with further embodiments of theinvention, may in general conveniently be added to the slurry andhomogenized therewith before drying.

Entirely aside from considerations of catalysts, the products made asdescribed have substantial utility as adsorbents, for example forclarification of fluids; and as desiccants.

At this stage, the catalyst material will contain some water, the amountlargely dependent upon the drying conditions, and most of theexchangeable cation sites will be occupied by ammonium ion. Thismaterial is then calcined at a temperature which optimally is 1,300F. toabout 1,500F. At the highest temperature just mentioned, there is someloss in catalytic effectiveness as compared with the same material driedat 1,300F. The calcining has the effect of dehydrating the material andat the same time decomposing the ammonium ion to ammonia gas which isdriven off and hydrogen cation which remains in the material. Thecalcination also brings about some modification of the mineral speciespresent, as discussed hereinbelow.

The so-c'alcined material is then of high utility as a crackingcatalyst, although I prefer to first subject the calcined material to asteam treatment for several hours at a like temperature, such as l.350F.for 8 hours in an atomsphere of steam at 15 pounds per square inchgauge. The steam-treated material is then preferably recalcined at alike temperature. such as 1.300F., for several hours. such as 4 hours.The material so produced is as a general rule even better as ahydrocarbon cracking catalyst. It needs no added binder, the clay-likemineral serving to produce coherent particles having adequate mechanicalstability.

As those skilled in the art will recognize. both the synthetic clay-likemineral and the faujasite possess cations which are not a permanent partof the crystal lattice but which may be exchanged for others, but whichare necessary for electrostatic neutrality of the substance as a whole.The silicate substance component likewise has a content of exchangeablecations, which for example is relatively low for kaolin and relativelyhigh for montmorillonite. When I speak of placing the substance in theammonium form, 1 refer to cxchanging any other cations which may beoriginally present. such as sodium. or sodium and calcium and the like.by ammonium ion. Also. when 1 refer to ammonium ion. 1 mean to includeammonium derivatives which are small enough to fit into the lattice andwhich will decompose under calcination in the same fashion to leavesolely residual hydrogen cation. Typical such ammonium derivatives aremethylammonium. trimetbylammonium. ethylammonium. and the like. Ingeneral I prefer ordinary ammonium ion. in view of its simplicity.effectiveness, availability. and low cost, and as will be seen below.the synthetic clay-like mineral is generally originally produced in itsammonium form.

Coming now to the synthetic clay-like mineral in more detail. theproduction and properties of one species of this substance are fullydescribed in the aforesaid U.S. Pat. Nos. 3.252.757 and 3.252.889. whichare hereby incorporated herein by reference. As initially produced. thissynthetic mineral substance has some water associated with the crystallattice. and furthermore as ordinarily made has its exchangeable cationinitially as ammonium. If any other cation is present instead. it may beconverted to the ammonium form. by known methods. an instance of whichappears in Example 4 of U.S. Pat. No. 3.252.757. This first species ofsynthetic clay-like mineral in its ammonium form may be described ashaving the following empirical formula:

nSiO- ,:Al O;,:mAB:.\'H O where the layer lattices comprise said silica.said alumina. and said B. and where n is from 2.4 to 3.0. m is from 0.2to 0.6.

A is one equivalent of ammonium cation and is external to the lattice.

B is chosen from the group of negative ions which consists of F. OH". V2and mixtures thereof. and is internal in the lattice. and

x is from 2.0 to 3.5 at 50 percent relative humidity. said mineral beingcharacterized by a d spacing at said humidity within the range whichextends from a lower limit of about 10.4 A. to an upper limit of about12.0 A.

The second species of synthetic clay-like mineral in its ammonium formmay be described as having the following empirical formula:

wherein the layer lattices comprise said silica, said alumina, and saidB, and where n is more than 1.8 but less than 2.4,

in is from 0.4 to 0.8.

A is one equivalent of ammonium cation and is external to the lattice.

B is chosen from the group of negative ions which consists of F, OH, V20' and mixtures thereof, and is internal in the lattice, and

.r is from 2.0 to 3.5 at 50 percent relative humidity, said mineralbeing characterized by a d spacing at said humidity within the rangewhich extends from a lower limit of about 10.4 A. to an upper limit ofabout 12.0 A.

As obtained, and as added to the slurry, this synthetic clay-likemineral is of such a fine particle size that it need not be ground.

After the calcining step. in the course of which both ammonia and waterare lost. the calcined synthetic clay-like mineral has a compositionwhich may be characterized as having the empirical formula, for thefirst species thereof:

wherein the layer lattices comprise said silica (SiO- said alumina (A1 0and said B;

wherein A is one equivalent of hydrogen, and wherein B is one equivalentof an anion selected from the group consisting of fluoride. hydroxyl,and oxygen ions. and mixtures thereof; said crystalline material beingfurther characterized by a d spacing ranging from 9.6 to 10.2 Angstromunits determined at 50 percent relative humidity and being predominantlyordered in two dimensions. Likewise. after the described calcining step.the second species of the synthetic clay-like material will have thefollowing empirical formula:

wherein the layer lattices comprise said silica (SiO- said alumina (Al-0:1) and said B;

wherein k is greater than 1.8 but less than 2.4; wherein A is oneequivalent of hydrogen. and

wherein B is one equivalent of an anion selected from the groupconsisting of fluoride. hydroxyl, and oxygen ions. and mixtures thereof:

said crystalline material being further characterized by a 11 spacingranging from 9.6 to 10.2 Angstrom units determined at 50 percentrelative humidity and being predominantly ordered in two dimensions.

Returning now to the two species of the synthetic clay-like material,the first species may be made in accordance with the instructions foundin the two patents cited, viz.. U.S. Pat. Nos. 3.252.757 and 3.252.889.The second species. in which the silica-to-alumina molar ratio liesbetween 1.8 and 2.4. may be made by modifying the directions for thepreparation of the first species. as follows:

Referring to the general formulation given hereinabove for the secondspecies. the Si0 and A1 0 components should be in a molar ratio of fromabout 1.8 to less than 2.7. depending upon the composition desired inthe final product. The molar rati of the anion B in the formulationgiven to alumina is correspondingly inversely within the range of about0.8 to about 0.4. As the selected silica to alumina ratio becomes lower.and thus as the molar ratio of B to alumina becomes higher. inaccordance with the foregoing. l find it useful to add AB in the form ofa mixture of NH.,F HF and NH.()H in such proportions that the F/SiO-molar ratio approximates 0.1 The inclusion of fluoride ion. particularlyat the lower silica/alumina ratios, expedites crystallization from thereaction mixture.

The first and second species are distinguished not only by theirrespective silica-to-alumina ratio ranges, but hand-in-hand with thesetwo ranges there is exhibited a striking difference in behavior whentreated with ethylene glycol. The following table shows the basalspacings obtained by x-ray diffraction on a series of syntheses of thelaminar-clay-like mineral in which the silica-to-alumina ratio wasvaried from about 2.2 to 2.6, and thus bridging the ranges for bothspecies. The treatment with ethylene glycol and the x-ray diffractiondeterminations were made in the conventional fashion. as described forexample in the book by George Brown (editor). The X-Ray Identificationand Crystal Strut-- !urex of (lay Minerals. London, 1961. At the sametime. x-ray diffraction determinations were made on the untreatedsamples which however had been permitted to come to equilibrium at roomtemperature in an atmosphere of 50 percent relative humidity.

The striking difference in behavior between thctwo species is evidentfrom the last column of the above table. 1n going from an SiO /A1 Oratio of 2.22 to 2.30, there is a small increase in spacing, all withinthe range of 12.2 to 12.7 A. However. by the time a ratio of 2.40 hasbeen reached. a sudden jump to a spacing of more than 17 A has takenplace. and increasing the ratio above 2.40 does not result in anyspacing larger than 17 to 18 A. 1 am not aware of the reasons for thisdiscontinuity in the glyeolated spacing as between the two species; acritical difference in charge balance may exist above which onemodification is stable. and below which the other is stable.

The faujasite may be natural. as already mentioned. although acommercial source of natural faujasite in quantity has apparently notyet been found. so that it is preferable to make it synthetically. Manyprocedures for this have been published. most generally in the patentliterature. as for example US. Pat. Nos. 3.130.006. 3.130.007.3.338.672. and others. Synthetic faujasite having the specifiedsilica-alumina ratio is commercially available under the fanciful nameofZeolite Y Here again, the synthetic faujasite. while crystalline. isgenerally minute in particle size. and only exceptionally will need tobe ground to suitable fineness for slurrying. Should any extensivenatural deposit be found. it is possible that the crystallinity will bewell developed so that grinding will be desirable.

Coming now to the silicate substance component. already noted, this maycomprise kaolinite, metakaolinite. halloysite, metahalloysite, andmontmorillonite, and mixtures of any or all of these in any desiredrelative proportion. These are all clay minerals and are obtainablecommercially, and when converted to their ammonium form require nospecial comminution for reduction to a fine particle size for slurrying.It may be noted that kaolinite, metakaolinite, halloysite, andmetahalloysite have quite low cation-exchange capacity. so thatconversion of these to the ammonium form, while desirable. is notessential.

In preparing a slurry of the three (or more) ingredients. no specialprecautions need to be observed. except to be sure that the particlesize of the individual components is lower than about three or fourmicrons or at least reduceable to that size in the course of theslurrying and agitation; and to agitate the slurry enough to bring abouta thorough intermixing of the particles. so that when a dried particleof say 50 microns diameter is eventually produced and formed, it willhave the same mineral composition as the bulk of the slurry and thuswill comprise a very large number of the component mineral particle allin intimate mutual contact. The total mineral interface area isaccordingly. very large. The water content of the slurry is notcritical; enough water should be present to result in a pumpable andagitatable slurry. A substantially higher water content than this doesno harm but reduces the throughput of any given drying apparatus usedfor drying the slurry. As already mentioned. any conventional methods ofdrying may be employed. and if spray drying which gives an optimumparticles size is not used. conventional grinding apparatus may be usedto obtain it.

Returning now to the calcined product. the composition of the calcinedclay-like mineral has already been noted. The faujasite retains itsfundamental framework structure. The other mineral species which arepresent undergo some change. in addition to the loss of ammonia andwater already mentioned. The starting and resulting species are asfollows:

An example will now be given of some compositions within the scope ofthe invention, in which the laminar clay-like mineral prepared and usedwas of the second species described. That is. it had a silica-to-aluminaratio which was less than 2.4 but more than 1.8. and in the presentinstance. it was 2.30.

An aqueous solution of polysilicic acid having an SiO content of 5.3percent; commercial alumina. Alcoa (-3 1 having an A1 0 content of 69.4percent; commercial NH F H assaying 96 percent; and commercial ammoniumhydroxide assaying 58.8 percent. were combined in suitable relativeproportions to give a feed composition having the following molarratios:

7 8 Sim/A1 2.4 TABLE III F/SiO 0.l

Composltlon "/1 Conversion '7? Gasoline NIL/M203 0.55

45% clay-like rnmeral 457. kaolinite 72.4 44.7

107! faujasite 45'7r clay-like mineral 45% halloysite 69.6 45.4 Thismixture, which had a pH of 9.0, was placed in mineral an autoclave,heated to 300C, maintained at this teml0 452/1 montmorillonite 62.7 489perature for three hours, and allowed to cool in the autoclave. Theheatup time was 13 hours, and the cooling 60.1 38.9 time was overnight.The product had a pH of 7.2, and' faulus'm a 2/Al O ratio of 2.30. Inthe table above, the percent conversion is the vol- The synthetlcClay-[Ike mmerill thus P p was ume percent conversion of cetane to allproducts, cormixed with an equal weight of kaolinite and 22.2 percent ofits weight of commercial faujasite having a silicazalimina ratio of4.87, and which had been ionexchanged to the ammonium form. The threeingredients were thus in the relative weight proportions of 45:45:10.The synthetic clay-like mineral was used in its slurry form asdischarged from the autoclave, without drying. After the kaolinite andthe faujasite had been added to this slurry in the proportions alreadygiven, the mixture was vigorously agitated in a commercial mixer, viz.,an Eppenbach mill. After agitation. a slurry was filtered, dried at105C, ground to approximately 30 to 60 mesh, and then calcined atl,300F. for 4 hours. The calcined material was then steam aged at1,350F. for 8 hours, in an atmosphere of steam at 15 pounds per squareinch gage. This aged material was then recalcined at 1,300F. for 4hours.

Similar compositions were made up in the same proportions as theforegoing, except that for the kaolinite there were substituted,variously, halloysite, and montmorillonite which had been ion-exchangedto the ammonium form. As explained previously, the baseexchangecapacities of kaolinite and halloysite are sufficiently low that thesewere not converted, but the montmorillonite was. The sequence of mixing,filtering, drying, calcining, steam aging, and recalcining was carriedout precisely as described for the kaolinite-bearing mixture.

In all cases, the compositions obtained were in the form of essentiallyspherical particles, with about 85 percent by weight of the particlesfalling within the particle size range of microns to 80 microns indiameter.

The results of tests to determine the cetane cracking behavior at 500C.of the product thus obtained are given below, and for comparison similardata are given for a mixture of 90 percent kaolinite and 10 percent offaujasite.

rected to 100 percent weight balance. The per cent gasoline is thevolume per cent conversion of cetane to gasoline, again corrected to 100percent weight balance.

It may be seen that the tripartite compositions in accordance with theinvention give a substantial increase in gasoline yield as well as inthe total per cent of conversion, as compared with a controlledcomposition in which, in effect, an equal weight of kaolinite wassubstituted for the synthetic clay-like mineral.

EXAMPLE 2 As a further example of compositions in accordance with theinvention, a synthetic clay-like mineral was made up substantially inaccordance with Example 1 of US. Pat. No. 3,252,757, although using asubstantially larger batch. The SiO /Al O ratio of the product was 2.55.This was made up into a tripartite composition following the proceduregiven in Example 1 hereinabove, the ingredients being 45 percent of thesynthetic clay-like mineral just described; 45 percent metakaolin; and10 percent of commercial faujasite having a Si- O /Al O ratio of 4.87,and which had been previously ion-exchanged so as to be in the magnesiumammonium form, the molar ratio of magnesium to ammonium beingapproximately 1:1.

Tests were carried out in a small scale fluid cracking apparatus incomparison with a widely sold commercial cracking catalyst said andbelieved to contain 10 percent high silica faujasite. The feed was anactual charge stock used in a large oil refinery for fluid catalyticcracking, having an AP] gravity of 25.7, an aniline point of l79F., andconsisting of approximately percent saturated hydrocarbons andapproximately 42.4 percent aromatic hydrocarbons. Results obtained inthe test runs for both the composition in accordance with the inventionand the commercial catalysts were as follows, two runs for each catalystbeing shown:

TABLE IV -Continued I Commercial Inventive C A l'ALYS'l: CatalystComposition Conversion. Pct. by

Vol. of Fresh Feed (100-Gas Oil 67.3 74.8 79.0 89.0 Yields, Pct. by Vol.of Fresh Feed (corr. to 100 Pct. Wt. Balance) Debut. Gasoline Dist: 51.656.7 60.0 64.2 ButaneButene 12.8 14.0 15.0 16.4 Propane-Propylene 8.68.6 9.7 10.9 Motor Octane Numhcrs Clear: 79.3 79.5 80.7 80.1 3 cc Tel:85.7 86.3 87.4 87.3

In the table above, the first and third columns represent single-passruns, whereas the second and fourth columns represent recycleoperations.

From the above results, it will be seen that the inventive compositionsubstantially outperformed the com mercial catalyst, in giving higherpercent conversion, higher percent gasoline, higher octane numbers, andenhanced response to tetraethyl lead.

As has been mentioned earlier, the present invention includesmodifications in which additional substances are present, generally inrelatively minor amount, which most generally enhance the effectivenessof the inventive compositions as catalysts. ln Example 2 hereinabove,the magnesium ion present in substantially equal molar amount with theammonium ion in the catfaujasite as a separate operation. Calcium ionmay likewise be employed with or in place of the magnesium ion. 1n anycase, the effects of this incorporation are most beneficial, as willappear from the following example:

EXAMPLE 3 before. The silica/alumina ratio of the product was 2.23.

This synthetic clay-like mineral was mixed with an ion exchangepositions on the faujasite helps to stabiequal weight of kaolinite andvarying percentages by lize the latter against the long-term effects ofhigh temtotal weight of the composition of a high silica faujasiteperatures. In accordance with a further embodiment of having asilica/alumina mol ratio of 4.87. In one series my invention, 1 mayincorporate a minor amount of of experiments, the faujasite waspreliminarily cationrare earth metal cations, which may alternatively beexchanged with rare earth cations and ammonium catemplaced on thefaujasite or on the synthetic clay-like ions to give a content of 0.85milliequivalents per gram mineral, by the usual cation exchangetechniques. 1f deof rare earth cations and 2.1 milliequivalents per gramsired, one may add the rare earth metal cations in the of ammonium ions.In another series of samples, the form of a suitable salt thereof to theslurry containing faujasite was cation exchanged so as to contain 1.9milthe synthetic clay-like mineral, the silicate substance,liequivalents per gram of magnesium ion and 0.95 milliand the faujasite.In this fashion, the rare earth metal equivalents per gram of ammoniumion. The compocations have full access to all of the exchange positionsnents were mixed together with water so as to form a in all of thesubstances present. It has not been deterslurry, which was then furthertreated as described for mined what distribution of the rare earth metalcations Example 1, resulting in a calcined, steam-aged catalyst. takesplace as between the faujasite and the clay-like In an additional seriesof tests, the same synthetic minerals, and mineral, also themontmorillonite in the clay-like mineral was mixed with the kaolinite ina event that that is present as the silicate substance or one of theseveral silicate substances used in the mix. In general, however. Iprefer to exchange the rare earth metal cations, and the magnesium ionsif used, onto the kaolinite/clay mineral ratio of 5:1. The faujasite wasexchanged with various cations as already described.

Cracking tests on the various samples made up in accordance with theforegoing gave the following results:

TABLE V Cracking Data for K 8, Matrix -1- Various Wt.7z FaujasiteComparison of RE- and MgNH -stabilization TABLE v1 Cracking Data for K-,B Matrix Various Wt. 71' Faujasite Comparison of RE-andMgNH,-Stabilization in the above tables, K 3, and K B stand respectivelyfor the mixtures in which the kaolinite-synthetic clay ratios were 1:1and 5:1.

Conditions of the cracking runs were essentially the same as those notedfor Example 1 hereinabove.

The favorable percent conversion obtained as well as the percentgasoline, here expressed as a fraction, may be noted.

Also, in the tables, -ane/-ene is the ratio of isobutane of the sum ofisobutylene plus butene-l, in the cracked product; coke selectivity isthe grams of coke produced per gram of cetane cracked; and hydrogenselectively is the volume of hydrogen in liters (standard conditions)per gram of cetane cracked.

When rare earth cations, magnesium ions, or any mixture of these areemplaced upon the faujasite, a wide range in concentration may be used.Thus, in general less than about 2 percent of the total cation exchangecapacity of the faujasite will result in a scarcely appreciableamelioration; whereas more than 100 percent of the cation exchangecapacity of the faujasite can be utilized only with difficulty. Thus, apractical range for this substitution is from 2 to 100 percent of thecation exchange capacity of the faujasite, whether the exchange is madeon the faujasite initially or to several components of the composition,particularly when in slurry form, as heretofore described. The relativeconcentration of the cations among the several species names is notcritical. As already mentioned, magnesium or calcium or rare earth ionsmay be utilized separately or in any combination thereof.

The faujasite further may be of the so-called ultrastable" variety. Thisvariant is described and explained in the paper by Ambs and Flankentitled Thermal Behavior of Synthetic Faujasite", Journal of Catalysisl4, 1 18-125 1969). The aforesaid article is hereby incorporated hereinby reference, together with the papers cited in the bibliographythereof, which appears on pages 124 and 125.

It will be understood that while 1 have explained the invention with theaid of numerous specific examples, nevertheless considerable variationis possible in choice of raw materials, proportions, processingconditions, and the like, within the broad scope of the invention as setforth in the claims which follow:

Having described the invention, 1 claim:

1. A composition of matter adapted for the production of hydrocarboncracking catalyst consisting essentially of coherent particles of anintimate intermixture of from about 15 to about 80 percent by weight ofa synthetic clay-type mineral selected from the class consisting of afirst species having the composition:

where the layer lattices comprise said silica, said alimina and said B,and where n is from 2.4 to 3.0, m is from 0.2 to 0.6,

I A is one equivalent of ammonium cation and is extersaid mineral beingcharacterize by a 11 spacing at said humidity within the range whichextends from a lower limit of about 10.4 A. to an upper limit of about12.0 A;

and of a second species having the composition:

where the layer lattices comprise said silica, said alumina, and said B,and where n is more than 1.8 but less than 2.4,

m is from 0.4 to 0.8,

A is one equivalent of ammonium cation and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH, /2O and mixtures thereof, and is internal in the lattice, and

.v is from 2.0 to 3.5 at 50 percent relative humidity, said mineralbeing characterized by a d spacing at said humidity within the rangewhich extends from a lower limit of about 10.4 A. to an upper limit ofabout 12.0 A.

and, mixtures thereof;

from about 1 to about 40 percent of faujasite having a silica-aluminaratio within the range of about 3 to about 6 /2;

and from up to about 70 percent of a silicate material chosen from theclass consisting of kaolinite, metakaolinite, halloysite,metahalloysite, montmorillonite, and mixtures thereof.

2. A process for the production of the composition of matter of claim 1which comprises admixing the individual components in comminuted formwith sufficient water to form a slurry therewith, agitating said slurryuntil compositional homogeneity is obtained therein, and thereafterdrying said slurry so as to produce solid particles having anessentially spherical form and exhibiting said compositional homogeneitywithin said particle.

'3. A hydrocarbon cracking catalyst consisting essentially of coherentparticles, said particles consisting essentially of an intimateintermixture of from about to about 80 percent by weight of a syntheticclay-type mineral selected from the class consisting of a first specieshaving the composition:

2.4 to 3.0 SiO :Al O :0.2 to 0.6 AB

wherein the layer lattices comprise said silica, said aluand of a secondspecies having the composition:

wherein the layer lattices comprise said silica, said alumina and saidB;

wherein k is greater than 1.8 but less than 2.4; wherein A is oneequivalent of hydrogen, and wherein B is one equivalent of an anionselected from the group consisting of fluoride, hydroxyl, and oxygenions, and mixtures thereof; said clay-type mineral being furthercharacterized by a d spacing ranging from 9.6 to 10.2 Angstrom unitsdetermined at 50 percent relative humidity and being predominantlyordered in two dimensions,

and mixtures thereof;

from about 1 to about 40 percent of faujasite having a silica-aluminaratio within the range of about 3 to about 6%;

and from 5 up to about percent of a silicate material chosen from theclass consisting of metakaolinite, metahalloysite, montmorillonite, andmixtures thereof.

4. A catalyst in accordance with claim 3 wherein said faujasite isselected from the class consisting of decationized faujasite andfaujasite containing cations selected from the class consisting ofhydrogen, magnesium, calcium, rare earth metal cations, and mixturesthereof.

5. A catalyst in accordance with claim 4 in which said magnesium,calcium, and rare earth metal cations are present in a total amount .offrom about 2 to about percent of the total cation exchange capacity ofsaid faujasite.

6. A process for the production of a hydrocarbon cracking catalyst whichcomprises the step of calcining the composition of matter of claim 1 ata temperature within the approximate range of about l,200F. to about1.500F. until said composition is substantially free of water andammonia.

7. The process in accordance with claim 6 in which said calcining stepis followed by treating with steam for a plurality of hours at atemperature within the range specified for said calcining step.

1. A COMPOSITION OF MATTER ADAPTED FOR THE PRODUCTION OF HYROCARBONCRACKING CATALYST CONSISTING ESSENTIALLY OF COHERENT PARTICLES OF ANINTIMATE INTERMIXTURE OF FROM ABOUT 15 TO ABOUT 80 PERCENT BY WEIGHT OFA SYNTHETIC CLAY-TYPE MINERAL SELECTED FROM THE CLASS CONSISTING OF AFIRST SPECIES HAVING THE COMPOSITION:
 2. A process for the production ofthe composition of matter of claim 1 which comprises admixing theindividual components in comminuted form with sufficient water to form aslurry therewith, agitating said slurry until compositional homogeneityis obtained therein, and thereafter drying said slurry so as to producesolid particles having an essentially spherical form and exhibiting saidcompositional homogeneity within said particle.
 3. A hydrocarboncracking catalyst consisting essentially of coherent particles, saidparticles consisting essentially of an intimate intermixture of fromabout 15 to about 80 percent by weight of a synthetic clay-type mineralselected from the class consisting of a first species having thecomposition: 2.4 to 3.0 SiO.sub.2 :Al.sub.2 O.sub.3 :0.2 to 0.6 ABkSiO.sub.2 :Al.sub.2 O.sub.3 :0.4 to 0.8 AB
 4. A catalyst in accordancewith claim 3 wherein said faujasite is selected from the classconsisting of decationized faujasite and faujasite containing cationsselected from the class consisting of hydrogen, magnesium, calcium, rareearth metal cations, and mixtures thereof.
 5. A catalyst in accordancewith claim 4 in which said magnesium, calcium, and rare earth metalcations are present in a total amount of from about 2 to about 100percent of the total cation exchange capacity of said faujasite.
 6. Aprocess for the production of a hydrocarbon cracking catalyst whichcomprises the step of calcining the composition of matter of claim 1 ata temperature within the approximate range of about 1,200.degree.F. toabout 1,500.degree.F. until said composition is substantially free ofwater and ammonia.
 7. The process in accordance with claim 6 in whichsaid calcining step is followed by treating with steam for a pluralityof hours at a temperature within the range specified for said calciningstep.